Design of metal ion-selective reagents for recovery of precious metals
- Authors: Moleko-Boyce, Pulleng
- Date: 2019
- Subjects: Bioinorganic chemistry , Metal complexes Speciation (Chemistry)
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/42510 , vital:36664
- Description: The study is divided into two sections; namely, (1) the design of rhodium(III) specific chelating ligands (tridentate bis-benzimidazole derivatives), and (2) the development of iridium(IV)-specific quaternary diammonium cations with electron donating and electron withdrawing groups. Bis-benzimidazole chelating ligands used were bis((1H-benzimidazol-2-yl)methyl)amine (NNN1), bis((1H-benzimidazol-2-yl)ethyl)amine (NNN2), bis((1H-benzimidazol-2-yl)methyl)sulfide (NSN1) and bis((1H-benzimidazol-2-yl)ethyl)sulfide (NSN2). Quaternary diammonium cations used were tetramethylbenzyl-1,10-diammonium chloride (QuatDMDAMeBnz), tetrabenzyl-1,10-diammonium chloride (QuatDMDABnz), tetratrifluoromethylbenzyl-1,10-diammonium chloride (QuatDMDACF3Bnz) and tetranitrobenzyl-1,10-diammonium chloride (QuatDMDANO2Bnz). For both studies, polyvinylbenzylchloride (PVBC) nanofibers were used as support material. The PVBC nanofibers which were functionalised with bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated for the selectivity for Rh(III) over Ir(III), Pt(II), Pd(II) and Ni(II), and for separation of Ir(IV) from Rh(III), respectively. The sorbent materials were characterised by FTIR, SEM, BET surface area, TGA, EDS and elemental analysis, and the results showed that the functionalization of the sorbent materials was successful.The efficiency of bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated in a column study under dynamic flow adsorption conditions. The adsorption kinetics and isotherms were investigated under batch conditions and fitted on pseudo-first-order and pseudo-second-order model, and Freundlich and Langmuir isotherm, respectively. It was observed that the bis-benzimidazole derivatives showed uptake of [RhCl3(H2O)3], and the loading capacities were observed in the following order; NSN1 (181.06 mg/g) > NSN2 (148.55 mg/g) > NNN1 (131.88 mg/g) > NNN2 (75.87 mg/g). The bis-benzimidazole derivatives preference for metal ions was further investigated with a multi-element solution containing Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II). The bis-benzimidazole derivatives showed the following order of loading capacity: NSN1 (47.28 mg/g) > NSN2 (23.89 mg/g) > NNN1 (17.47 mg/g) > NNN2 (14.91 mg/g) for Rh(III); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NNN2 (33.96 mg/g) > NSN1 (30.95 mg/g) > NSN2 (19.95 mg/g) > NNN1 (14.92 mg/g) for Pt(II); NNN1 (47.94 mg/g) > NNN2 (28.90 mg/g) > NSN1 (16.22 mg/g) > NSN2 (15.83 mg/g) for Pd(II). Bis-benzimidazole derivatives showed no uptake of nickel(II) under these conditions. It was observed the ligand-selectivity order for Rh(III) was similar in both single-element and multi-element studies. This order showed that the bis-benzimidazoles containing a sulfur atom showed a high preference for rhodium(III) compared to Pt(II) which had a high preference for NNN2 as well as Pd(II) which had a high preference for NNN1. Ir(III) generally had a lower preference for the ligands presumably due to its higher kinetic inertness compared with Rh(III). Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- on nanofibers functionalized with diammonium cations was carried out and the loading capacities of [IrCl6]2- were obtained. [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The loading capacities of [IrCl6]2- with the quaternary diammonium sorbent materials increased in the order of F-QuatDMDAMeBnz (60.29 mg/g) < F-QuatDMDABnz (67.61 mg/g) < F-QuatDMDACF3Bnz (107.59 mg/g) < F-QuatDMDANO2Bnz (140.47 mg/g). The loading capacity for Ir(IV) with quaternary diammonium cationic nanofibers increased with an increase in the electron-withdrawing nature of the quaternizing group. The charge delocalizing ability of the nitrobenzyl group resulted in the best interaction of the diammonium cation with [IrCl6]2-. Batch equilibrium studies were carried out to assess the efficiency of bis-benzimidazole chelating derivatives as adsorbents using a multi-metal solution (Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II)) in 0.5 M HCl. The efficiency of the quaternary diammonium cations was tested using a binary metal solution (Ir(IV) and Rh(III)) in 6 M HCl. The isothermal batch adsorption studies of a multi-metal solution with bis-benzimidazoles derivatives fitted the Langmuir isotherm model which confirmed monolayer adsorption onto a homogeneous surface. The Langmuir isotherm parameter (qe (mg/g)), using functionalized nanofibers, showed the order of NNN2 (128.21 mg/g) > NSN1 (99.01 mg/g) > NSN2 (91.74 mg/g) > NNN1 (84.03 mg/g) for Pt(II); NNN1 (66.23 mg/g) > NNN2 (5.89 mg/g) > NSN1 (1.40 mg/g) > NSN2 (0.59 mg/g) for Pd(II); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NSN1 (140.85 mg/g) > NSN2 (109.89 mg/g) > NNN1 (104.17 mg/g) > NNN2 (91.74 mg/g) for Rh(III). The pseudo-first-order kinetics model was found to be the best fit to describe the adsorption kinetics of all metal ions onto all the sorbent materials. K1 (min-1) value in pseudo-first-order kinetics showed the same order of adsorption as observed in the Langmuir isotherms. The isothermal batch adsorption studies of [IrCl6]2- and [RhCl5(H2O)]2- with quaternary diammonium cations fitted the Freundlich isotherm model and confirmed to be effective for multiple-layered adsorption onto a heterogeneous surface. The Freundlich isotherm parameter (kf (mg/g)) using functionalized quaternary diammonium cationic nanofibers increased in the order of F-QuatDMDANO2Bnz (794.33 mg/g) > F-QuatDMDACF3Bnz (185.35 mg/g) > F-QuatDMDABnz (156.32 mg/g) > F-QuatDMDAMeBnz (112.46 mg/g) for Ir(IV) uptake. F-QuatDMDANO2Bnz resin showed the highest adsorption than that of F-QuatDMDAMeBnz, F-QuatDMDABnz and F-QuatDMDACF3Bnz and this order is similar to what was observed in column studies. The quaternary diammonium cations were shown to have the highest adsorption capacity for Ir(IV) compared with Rh(III). The adsorption of Rh(III) was also observed to increase in the order of F-QuatDMDANO2Bnz (177.83 mg/g) > F-QuatDMDACF3Bnz (40.37 mg/g) > F-QuatDMDABnz (36.98 mg/g) > F-QuatDMDAMeBnz (12.71 mg/g). The pseudo-second-order kinetic model was found to be the best fit to describe the adsorption kinetics of both metal ions onto all the sorbent materials. K2 (g.mg-1min-1) value in pseudo-second-order kinetics showed the same order of adsorption as observed in the Freundlich isotherms. The adsorption studies showed adsorption takes place via chemisorption process. This thesis presents PGMs and iridium-specific materials that could be applied in solutions of secondary PGMs sources containing rhodium, platinum and palladium with bis-benzimidazoles as well as in feed solutions from ore processing with diammonium cations for iridium recovery.
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- Date Issued: 2019
A bioinorganic investigation of some metal complexes of the Schiff base, N,N'-bis(3-methoxysalicylaldimine)propan-2-ol
- Authors: Mopp, Estelle
- Date: 2010 , 2012-04-13
- Subjects: Schiff bases , Bioinorganic chemistry , Metal complexes , Transition metal complexes , Transition metals , Cancer -- Chemotherapy , Ligands -- Toxicity , Antineoplastic agents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4413 , http://hdl.handle.net/10962/d1006768 , Schiff bases , Bioinorganic chemistry , Metal complexes , Transition metal complexes , Transition metals , Cancer -- Chemotherapy , Ligands -- Toxicity , Antineoplastic agents
- Description: This thesis includes the synthesis, characterisation, antioxidant and antimicrobial activities of Cu(II)-, Co(II)- and Co(III) complexes with N,N'-bis(3- methoxysalicylaldimine)propan-2-ol, 2-OH-oVANPN. The Schiff base ligand, 2-OHoVANPN, is derived from o-vanillin and 1,3-diaminopropan-2-ol. The o-vanillin condensed with 1,3-diaminopropan-2-ol in a 2:1 molar ratio yields this potential tetraor pentadentate ligand. The complexes synthesized are tetra (or penta or hexa) coordinated. Formation of the complexes is symbolized as follows:- MX₂ + 2-OH-oVANPN (2:1) -> [M(2-OH-oVANPN)Xn] + HnX MX₂ + 2-OH-oVANPN (2:1) -> [Mn(2-OH-oVANPN)OH] + H₂X₂ MX₂ + (o-vanillin : diaminopropanol) (1:1) -> [M(1:1)X₂] MX₂ + (o-vanillin : diaminopropanol) (1:1) -> [M₃(1:1)X₄] M = Cu(II), Co(II) or Co(III); X = Cl; n = 1, 2. Their structural features have been deduced from their elemental analytical data, IR spectral data, and electronic spectral data. With the exception of {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆}(A4), the Cu(II) complexes were monomeric with 2-OH-oVANPN acting as a tetradentate ligand. A binuclear Co(II) complex, [Co₂(C₁₉H₁₉N₂O₅)(OH)] (B1), was synthesised and the rest of the Co(II) and Co(III) complexes were monomeric with chloride ions coordinating to the metal centre in some cases. Electronic data suggest that the cobalt(II) complexes have octahedral geometries and the copper(II) complexes have square planar structures – Co(III) is likely to be octahedral. Thermal analyses, which included the copper-block-method for determining sublimation temperatures, revealed that some copper(II) and cobalt(II) complexes are hygroscopic and sublime at 200 °C and below. DSC analyses of the Cu(II) complexes gave exotherms around 300 °C for complexes K[Cu(C₁₉H₂₀N₂O₅)(OH)]·2H₂O (A1) and [Cu(C₁₁H15N₂O₃)(Cl)₂]·2H₂O (A2) and above 400 °C for [Cu(C₁₁H₁₆N₂O₃)(Cl)₂] (A3) and {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆} (A4). Antioxidant studies were carried out against the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·). The cobalt(II) complex, [Co₂(C₁₉H₁₉N₂O₅)(OH)] (B1), which was synthesized in the presence of KOH, had no antioxidant activity, whilst the other cobalt(II) complexes, [Co(C₁₇H₁₇N₂O₅(Cl))]·1½H₂O (B2), [Co(C₁₉H₂₂N₂O₅) (Cl)₂]·5½H₂O (B3) and [Co(C₁₉H₂₂N₂O₅)(Cl)₂]·5½H₂O (B4), which were synthesised in the absence of KOH, demonstrated antioxidant activity. The latter complexes are candidates for cancer cell line testing, while [Cu(C₁₁H₁₆N₂O₃)(Cl)₂] (A3), {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆} (A4), [Co(C₁₉H₂₁N₂O₅)(Cl)₂ ]·5H₂O (C2) and [Co(C₁₉H₂₀N₂O₅)(Cl)]·3H₂O (C3) may show anticancer activity through possible hydrolysis products. Most of the complexes synthesized displayed antimicrobial activity against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Aspergillus niger and Candida albicans. The results indicated that complexes [Cu(C₁₁H₁₆N₂O₃)(Cl)₂](A3), [Co(C₁₉H₂₂N₂O₅)(Cl)₂]·5½H₂O (B3) and [Co(C₁₉H₂₁N₂O₅)(Cl)₂ ]·5H₂O (C2) are active against the Gram-negative Ps. aeruginosa and that the ligand, 2-OH-oVANPN, did not have any activity. The same trend was observed with 2-OH-oVANPN, {Cu₃(C₁₁H₁₄N₂O₃)(Cl)4(H₂O)₆} (A4) and [Co(C₁₉H₂₀N₂O₅)(Cl)]·3H₂O (C3) against the Gram-positive S. aureus. As for activity against E. coli and C. albicans, some complexes showed more activity than the ligand. There is an observed trend here that the metal complexes are more active (toxic) than the corresponding ligand, which is in agreement with Tweedy’s chelation theory.
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- Date Issued: 2010